CN110917912B - Internal pressure type composite hollow fiber nanofiltration membrane yarn and preparation method thereof - Google Patents
Internal pressure type composite hollow fiber nanofiltration membrane yarn and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 193
- 239000012510 hollow fiber Substances 0.000 title claims abstract description 97
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 75
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims description 37
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 34
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 34
- 125000000524 functional group Chemical group 0.000 claims abstract description 6
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 6
- 239000004760 aramid Substances 0.000 claims abstract 2
- 229920003235 aromatic polyamide Polymers 0.000 claims abstract 2
- 238000004132 cross linking Methods 0.000 claims description 100
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 66
- 238000002791 soaking Methods 0.000 claims description 45
- 239000007788 liquid Substances 0.000 claims description 40
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000108 ultra-filtration Methods 0.000 claims description 30
- 229920000768 polyamine Polymers 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 18
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 17
- 238000005266 casting Methods 0.000 claims description 13
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 9
- 238000001223 reverse osmosis Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 8
- 239000012752 auxiliary agent Substances 0.000 claims description 7
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 229920002873 Polyethylenimine Polymers 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 4
- 238000009472 formulation Methods 0.000 claims description 4
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- 230000009471 action Effects 0.000 claims description 3
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- 238000007711 solidification Methods 0.000 claims description 3
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- 125000000542 sulfonic acid group Chemical group 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 230000007246 mechanism Effects 0.000 claims description 2
- 229920000083 poly(allylamine) Polymers 0.000 claims description 2
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- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 238000011049 filling Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 100
- 238000012360 testing method Methods 0.000 description 31
- 239000010410 layer Substances 0.000 description 24
- 238000003756 stirring Methods 0.000 description 18
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 16
- 230000004907 flux Effects 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 239000000460 chlorine Substances 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 239000003431 cross linking reagent Substances 0.000 description 8
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- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
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- 229910001425 magnesium ion Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012695 Interfacial polymerization Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229920002521 macromolecule Polymers 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
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- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
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- 229910052749 magnesium Inorganic materials 0.000 description 1
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- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
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- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
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- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/76—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74
- B01D71/82—Macromolecular material not specifically provided for in a single one of groups B01D71/08 - B01D71/74 characterised by the presence of specified groups, e.g. introduced by chemical after-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0013—Casting processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/08—Hollow fibre membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/58—Other polymers having nitrogen in the main chain, with or without oxygen or carbon only
- B01D71/60—Polyamines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides an internal pressure type composite hollow fiber nanofiltration membrane wire, which comprises an inner layer of a hollow fiber membrane taking polyether sulfone as a main body, wherein an amino functional group reacts with a catalyst to form an aromatic polyamide compact selective layer. The hollow fiber membrane component can realize a higher filling area which can reach 2-3 times of that of a roll-type membrane component, and the processing capacity can be greatly improved.
Description
Technical Field
The invention relates to the field of hollow fiber membranes, in particular to an internal pressure type composite hollow fiber nanofiltration membrane yarn and a preparation method thereof.
Background
Nanofiltration Membranes (nanofiltraction Membranes) were a new type of separation membrane that was made available at the end of the 80 s, with a molecular weight cut-off between reverse osmosis and ultrafiltration Membranes of about 200-. At present, roll-type nanofiltration membranes of various companies such as Dow, general electric and the like occupy the leading position in the market, the membranes are all composite membranes, and an interfacial polymerization and condensation method is adopted, and the preparation method is to compound a layer of ultrathin separation layer (TFC) with a nanometer-scale aperture on the surface of a thin-film polyimide microporous base membrane to prepare the membrane.
However, interfacial polymerization and condensation methods have many disadvantages such as high cost, low contamination resistance, low oxidant/free chlorine tolerance, and limited cleaning methods. One of the major drawbacks is that TFC membranes have a very high tendency to fouling, firstly, relatively less negatively charged surfaces and rough surfaces, and organic compounds are likely to adhere to or reside on the membrane surface due to chemical or physical reactions. Second, TFC composite membranes have low chlorine resistance. Typically, its free chlorine tolerance is below 500ppmh and the membrane cannot remain intact in solutions with free chlorine content exceeding 0.5 ppm. Therefore, composite nanofiltration membranes are limited in many applications by complex pretreatment measures. Last but not least, TFC membranes cannot be backwashed due to loose affinity between the TFC functional layer and the support layer.
In summary, ultra-thin separation layers (TFC) are poor in oxidation/free chlorine resistance/contamination resistance and are difficult to meet the market demand of nanofiltration membranes. The preparation of the composite nanofiltration membrane adopts a polyimide microporous base membrane, the oxidation resistance/free chlorine resistance/stain resistance of the composite nanofiltration membrane is poor, no relation occurs between interfacial polymerization and the base membrane in a two-step method, the base membrane and a coating layer have poor bonding property, and the composite nanofiltration membrane is only suitable for flat membranes and roll-up membranes.
Disclosure of Invention
The invention aims to provide an internal pressure type composite hollow fiber nanofiltration membrane and a preparation method thereof.
In order to achieve the purpose, the invention provides the following technical scheme:
the formula of the internal pressure type composite hollow fiber nanofiltration membrane yarn comprises a membrane casting feed liquid and a core liquid, wherein a crosslinking system comprises a first crosslinking solution and a second crosslinking solution;
the membrane casting feed liquid is prepared from hydrophilic macromolecules, a solvent and a feed liquid auxiliary liquid, wherein the hydrophilic macromolecules are selected from polyether sulfone, polysulfone or a material containing sulfonic groups, such as sulfonated polysulfone and sulfonated polyether sulfone, the content of the solute of the hydrophilic macromolecules is 5-30 wt%, and the molecular weight is between 500000-; wherein the solvent is at least one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and the feed liquid auxiliary agent comprises at least one of polyethylene glycol and polyvinylpyrrolidone.
The preparation of the casting film feed liquid is as follows: placing hydrophilic polymer, solvent and auxiliary agent into a dissolving kettle, stirring and dissolving for 24-48 hours at the temperature of 40-60 ℃ and the rotating speed of 100r/min, cooling to 20-30 ℃, and defoaming for 8-12 hours under the pressure of-0.09-0.08 MPa to obtain the casting solution.
The core liquid is prepared from a solvent, a non-solvent and an auxiliary agent, wherein the solvent comprises one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone, the non-solvent comprises one of water and ethanol, and the auxiliary agent comprises at least one of ethylene glycol and glutaraldehyde.
Preparing a core liquid: and (3) placing the solvent, the non-solvent and the auxiliary agent into a stirring kettle, stirring and mixing for 4 hours at the rotating speed of 100r/min, and defoaming for 2-4 hours under the pressure of-0.05 MPa to obtain the core liquid.
A preparation method of an internal pressure type composite hollow fiber nanofiltration membrane yarn comprises the following steps:
s1 preparation of hollow fiber ultrafiltration membrane:
and respectively injecting the casting membrane feed liquid and the core liquid into a spinning nozzle through a casting membrane liquid channel and a core liquid channel by a gear pump, extruding a hollow tubular liquid membrane through a casting membrane liquid port and a core liquid port of the spinning nozzle, allowing the hollow tubular liquid membrane to pass through an air section height and enter a solidification bath pool for solidification, soaking a desolventizing agent at constant temperature to obtain hollow fiber membrane filaments, and sequentially passing through water and glycerol in the hollow fiber membrane base membrane, then airing, and airing in the air to obtain the hollow fiber ultrafiltration base membrane.
S2, preparing a polyamine compact selective layer;
and forming a crosslinked polyamine compact selective layer on the skin layer of the hollow fiber ultrafiltration basal membrane through crosslinking, wherein the crosslinking system comprises a first crosslinking solution and a second crosslinking solution.
The forming mechanism of the crosslinked polyamine dense selective layer is that the polyamine polymer is uniformly coated on the inner surface of the hollow fiber membrane, and then the crosslinked polyamine polymer and glutaraldehyde in the second crosslinking solution are subjected to crosslinking reaction, the reaction equation is shown in figure 4, and the surface micrograph is shown in figure 3.
The formulation of the first crosslinking solution includes:
the composition of the three formulas is 100 percent according to the weight percentage: 0.1% -5% of first high molecular polymer, namely polyethyleneimine, polyallylamine, polyamide and the like; solvent-water: 95 to 99.9 percent; additives-sodium dodecyl benzene sulfonate, sodium dodecyl sulfonate and the like 0.01-0.05%;
the formulation of the second crosslinking solution comprises:
the combination of the two formulas is 100 percent according to the weight percentage: 0.1 to 20 percent of glutaraldehyde; solvent-water: 80 to 99.9 percent;
different from the traditional two-step method, the scheme adopts polyamine monomer to carry out polycondensation reaction under the action of a crosslinking agent, and has the advantages of short time, aqueous solution and simple operation.
Preparation process of the polyamine dense selective layer:
s21: preparing a first crosslinking solution and a second crosslinking solution according to a compact selective layer formula;
preparation of a crosslinking solution: and (3) placing the cross-linking agent and deionized water into a stirring kettle, stirring and mixing for 2 hours at the rotating speed of 60-80r/min, and standing for 1 hour to obtain a cross-linking solution.
S22: soaking the hollow fiber ultrafiltration base membrane obtained in the step S1 in a first cross-linking solution at the temperature of 15-35 ℃, taking out after soaking for 1-60 minutes, and removing the redundant first cross-linking solution;
s23: soaking the hollow fiber ultrafiltration base membrane treated in the step S22 in a second crosslinking solution at 15-35 ℃ for 1-60 minutes, taking out, and removing the redundant second crosslinking solution;
s24: immersing the hollow fiber ultrafiltration basal membrane treated in the step S23 in reverse osmosis water, controlling the temperature at 15-85 ℃, and taking out after immersing for 1-48 hours;
s25: immersing the hollow fiber ultrafiltration basal membrane treated in the step S24 in a glycerol solution, controlling the temperature at 15-45 ℃, and taking out after immersing for 12-48 hours;
s26: and (4) drying the hollow fiber ultrafiltration basal membrane treated in the step S25 in air at the temperature of 20-30 ℃ to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
According to the invention, the internal pressure type composite hollow fiber nanofiltration membrane wire comprises a hollow fiber base membrane prepared from polyether sulfone, polysulfone or a material containing sulfonic acid groups, wherein a polyamine compact selection layer obtained by reacting an amino functional group with glutaraldehyde is formed on the surface layer of the hollow fiber base membrane.
Compared with the prior art, the technical scheme has the following characteristics and beneficial effects: the internal pressure type composite hollow fiber nanofiltration membrane wire comprises an inner layer of a hollow fiber membrane taking polyether sulfone as a main body, and a polyamine compact selective layer is formed by amino functional groups and glutaraldehyde. The hollow fiber membrane component can realize a higher filling area which can reach 2-3 times of that of a roll-type membrane component, and the processing capacity can be greatly improved.
In the technical scheme, the polysulfone ultrafiltration base membrane is used as the base membrane, the oxidation resistance/free chlorine resistance/stain resistance are good, the cross-linking reaction is adopted, the binding force between the coating and the base membrane is strong, and the preparation method can also be suitable for preparing the hollow fiber membrane.
In addition, the membrane yarn can achieve a good divalent salt interception effect under the pressure of 2-5bar, the requirement of the membrane inlet pressure is far lower than that of the existing roll-type nanofiltration membrane on the market, the preparation formula is simple, the material and production cost are low, the process operation is simple, the large-scale production is easy, and the hollow fiber low-pressure nanofiltration membrane can be applied to the fields of life, environmental protection, chemical industry and the like.
Drawings
Fig. 1 to 3 are schematic views of microstructures of internal pressure type composite hollow fiber nanofiltration membrane filaments according to an embodiment of the present invention.
FIG. 4 is a reaction formula of a dense selective layer of polyamine according to the present invention.
Fig. 5 is a schematic structural diagram of a nanofiltration membrane test equipment according to an embodiment of the invention.
FIG. 6 is a graph showing the results of a repeatability test according to the present invention.
Fig. 7 is a graph showing the test results of the long-term stability test according to the present invention.
Fig. 8 is a graph showing the test results of the chlorine resistance test according to the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
It will be understood by those skilled in the art that in the present disclosure, the terms "longitudinal," "lateral," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," and the like are used in an orientation or positional relationship indicated in the drawings for ease of description and simplicity of description, and do not indicate or imply that the referenced devices or components must be constructed and operated in a particular orientation and thus are not to be considered limiting.
It is understood that the terms "a" and "an" should be interpreted as meaning that a number of one element or element is one in one embodiment, while a number of other elements is one in another embodiment, and the terms "a" and "an" should not be interpreted as limiting the number.
The internal pressure type composite hollow fiber nanofiltration membrane filament prepared by the scheme has a structure shown in fig. 1 and fig. 2, the inner layer is a hollow fiber ultrafiltration base membrane which takes polyether sulfone as a main body to form a polyamine compact selection layer, the hollow fiber ultrafiltration base membrane is in a spongy shape and allows high-flux water to pass through under low pressure, and the polyamine compact layer is formed on the inner wall of the base membrane, so that the aperture and the surface electrical property of the membrane are effectively controlled.
The following examples are given by way of illustration:
film preparation example one:
1. preparing a hollow fiber ultrafiltration basal membrane, wherein a membrane preparation system comprises feed liquid and core liquid.
According to the weight proportion, sequentially taking 24 parts of polyether sulfone, 30 parts of non-solvent and 46 parts of solvent, stirring and dissolving at the temperature of 50 ℃ in a reaction kettle, and defoaming for 12 hours in vacuum after 24 hours to obtain homogeneous feed liquid;
according to the weight proportion, 10 parts of solvent and 90 parts of water are sequentially taken to be stirred and dissolved in a reaction kettle for 4 hours at normal temperature, and then core liquid is obtained;
the feed liquid and the core liquid are respectively injected into a spinning nozzle through a film casting liquid channel and a core liquid channel by a gear pump, and a hollow tubular liquid film is extruded through a film casting liquid port and a core liquid port of the spinning nozzle. Then, the liquid film passes through an air gap of 10cm and then sequentially passes through two coagulation baths and then is wound on a wire winding wheel to form a hollow fiber nanofiltration membrane wire through phase change, and after post-treatment, the inner diameter and the outer diameter of the hollow fiber nanofiltration membrane wire are 0.6/1.1 mm.
2. Preparing a composite nanofiltration membrane:
and forming a crosslinked polyamine compact selective layer on the polyether sulfone base membrane by crosslinking, wherein the crosslinking system comprises a first crosslinking solution and a second crosslinking solution.
The formula of the first crosslinking solution comprises 5 percent of polyethyleneimine, 0.05 percent of sodium dodecyl benzene sulfonate and 94.95 percent of water; the formula of the second crosslinking solution is 5% of glutaraldehyde and 95% of water, the crosslinking agent and deionized water are placed in a stirring kettle, and the crosslinking solution is obtained after stirring and mixing for 2 hours and standing for 1 hour under the condition that the rotating speed is 60-80 r/min. Soaking the polyether sulfone base membrane in a first crosslinking solution at the temperature of 35 ℃, taking out the polyether sulfone base membrane after soaking for 30 minutes, and removing the redundant first crosslinking solution; soaking the treated polyether sulfone hollow fiber base membrane in a second crosslinking solution at the temperature of 35 ℃, taking out after soaking for 30 minutes, and removing the redundant second crosslinking solution; washing and soaking the mixture for 24 hours by reverse osmosis water and then taking out the mixture; and soaking in glycerol solution, and drying to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
Preparation example two:
1. the preparation of the hollow fiber ultrafiltration basal membrane is the same as that of the first preparation example;
2. preparing a composite nanofiltration membrane: and forming a crosslinked polyamine compact selective layer on the polyether sulfone base membrane by crosslinking, wherein the crosslinking system comprises a first crosslinking solution and a second crosslinking solution.
The formula of the first crosslinking solution comprises 2 percent of polyethyleneimine, 0.05 percent of sodium dodecyl benzene sulfonate and 97.95 percent of water; the formula of the second crosslinking solution is 3 percent of glutaraldehyde and 97 percent of water, the crosslinking agent and the deionized water are placed in a stirring kettle, and the crosslinking solution is obtained after stirring and mixing for 2 hours and standing for 1 hour under the condition of the rotating speed of 60-80 r/min. Soaking the polyether sulfone base membrane in a first crosslinking solution at the temperature of 35 ℃, taking out the polyether sulfone base membrane after soaking for 30 minutes, and removing the redundant first crosslinking solution; soaking the treated polyether sulfone hollow fiber base membrane in a second crosslinking solution at the temperature of 35 ℃, taking out after soaking for 30 minutes, and removing the redundant second crosslinking solution; washing and soaking the mixture for 24 hours by reverse osmosis water and then taking out the mixture; and soaking in glycerol solution, and drying to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
Preparation example three:
1. the preparation of the hollow fiber ultrafiltration basal membrane is the same as that of the first preparation example;
2. preparing a composite nanofiltration membrane:
and forming a crosslinked polyamine compact selective layer on the polyether sulfone base membrane by crosslinking, wherein the crosslinking system comprises a first crosslinking solution and a second crosslinking solution.
The formula of the first crosslinking solution comprises 8 percent of polyacrylamide, 0.04 percent of sodium dodecyl benzene sulfonate and 91.96 percent of water; the formula of the second crosslinking solution is 6 percent of glutaraldehyde and 94 percent of water, the crosslinking agent and the deionized water are placed in a stirring kettle, and the crosslinking solution is obtained after stirring and mixing for 2 hours and standing for 1 hour under the condition of the rotating speed of 60-80 r/min. Soaking the polyether sulfone base membrane in a first crosslinking solution at the temperature of 35 ℃, taking out the polyether sulfone base membrane after soaking for 30 minutes, and removing the redundant first crosslinking solution; soaking the treated polyether sulfone hollow fiber base membrane in a second crosslinking solution at the temperature of 35 ℃, taking out after soaking for 30 minutes, and removing the redundant second crosslinking solution; washing and soaking the mixture for 24 hours by reverse osmosis water and then taking out the mixture; and soaking in glycerol solution, and drying to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
Preparation example four:
1. the preparation of the hollow fiber ultrafiltration basal membrane is the same as that of the first preparation example;
2. preparing a composite nanofiltration membrane:
and forming a crosslinked polyamide compact selective layer on the polyether sulfone base membrane by crosslinking, wherein a crosslinking system comprises a first crosslinking solution and a second crosslinking solution.
The formula of the first crosslinking solution comprises 6 percent of polyamide, 0.05 percent of sodium dodecyl benzene sulfonate and 93.95 percent of water; the formula of the second crosslinking solution is 4% of glutaraldehyde and 96% of water, the crosslinking agent and deionized water are placed in a stirring kettle, and the crosslinking solution is obtained after stirring and mixing for 2 hours and standing for 1 hour under the condition that the rotating speed is 60-80 r/min. Soaking the polyether sulfone base membrane in a first crosslinking solution at the temperature of 35 ℃, taking out the polyether sulfone base membrane after soaking for 30 minutes, and removing the redundant first crosslinking solution; soaking the treated polyether sulfone hollow fiber base membrane in a second crosslinking solution at the temperature of 35 ℃, taking out after soaking for 30 minutes, and removing the redundant second crosslinking solution; washing and soaking the mixture for 24 hours by reverse osmosis water and then taking out the mixture; and soaking in glycerol solution, and drying to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
Comparative example one:
1. the preparation of the hollow fiber ultrafiltration basal membrane is the same as that of the first preparation example;
2. preparing a composite nanofiltration membrane: and forming a crosslinked polyamine compact selective layer on the polyether sulfone base membrane by crosslinking, wherein the crosslinking system comprises a first crosslinking solution and a second crosslinking solution.
The formula of the first crosslinking solution comprises 0.5 percent of polyethyleneimine, 0.05 percent of sodium dodecyl benzene sulfonate and 99.45 percent of water; the formula of the second crosslinking solution is 3 percent of glutaraldehyde and 97 percent of water, the crosslinking agent and the deionized water are placed in a stirring kettle, and the crosslinking solution is obtained after stirring and mixing for 2 hours and standing for 1 hour under the condition of the rotating speed of 60-80 r/min. Soaking the polyether sulfone base membrane in a first crosslinking solution at the temperature of 35 ℃, taking out the polyether sulfone base membrane after soaking for 30 minutes, and removing the redundant first crosslinking solution; soaking the treated polyether sulfone hollow fiber base membrane in a second crosslinking solution at the temperature of 35 ℃, taking out after soaking for 30 minutes, and removing the redundant second crosslinking solution; washing and soaking the mixture for 24 hours by reverse osmosis water and then taking out the mixture; and soaking in glycerol solution, and drying to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
Comparative example two:
1. the preparation of the hollow fiber ultrafiltration basal membrane is the same as that of the first preparation example;
2. preparing a composite nanofiltration membrane:
and forming a crosslinked polyamine compact selective layer on the polyether sulfone base membrane by crosslinking, wherein the crosslinking system comprises a first crosslinking solution and a second crosslinking solution.
The formula of the first crosslinking solution comprises 20 percent of polyethyleneimine, 0.05 percent of sodium dodecyl benzene sulfonate and 79.95 percent of water; the formula of the second crosslinking solution is 3 percent of glutaraldehyde and 97 percent of water, the crosslinking agent and the deionized water are placed in a stirring kettle, and the crosslinking solution is obtained after stirring and mixing for 2 hours and standing for 1 hour under the condition of the rotating speed of 60-80 r/min. Soaking the polyether sulfone base membrane in a first crosslinking solution at the temperature of 35 ℃, taking out the polyether sulfone base membrane after soaking for 30 minutes, and removing the redundant first crosslinking solution; soaking the treated polyether sulfone hollow fiber base membrane in a second crosslinking solution at the temperature of 35 ℃, taking out after soaking for 30 minutes, and removing the redundant second crosslinking solution; washing and soaking the mixture for 24 hours by reverse osmosis water and then taking out the mixture; and soaking in glycerol solution, and drying to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
Method for rejection test:
in addition, the performance of the internal pressure type composite hollow fiber nanofiltration membrane filament is detected on nanofiltration membrane test equipment, the structure of the nanofiltration membrane test equipment is shown in figure 5, a membrane component is obtained by preparing the internal pressure type composite hollow fiber nanofiltration membrane filament, the diameter of the detected membrane component is 15-100mm, the length of the detected membrane component is 200-400mm, and the effective membrane area is 0.09-2.5m2。
Because the compact selection layer is positioned at the inner side of the internal pressure type composite hollow fiber nanofiltration membrane yarn, the original solution can pass through the inner cavity side of the membrane component after circulating under the membrane inlet pressure of 2-5bar, and the produced water flows out from the outer cavity side of the membrane component.
Firstly, deionized water is used as a raw water solution to obtain the purified water permeability PWP of the internal pressure type composite hollow fiber nanofiltration membrane:
wherein F is the permeation flux (l/m)2h) Δ P is the transmembrane pressure drop (bar), Q is the volume permeate flow (l/h), A is the effective membrane filtration area (m)2)。
After about 1 hour of deionized water rinse, the membrane flux reached constant, and filtration tests were performed on the hollow fiber nanofiltration membranes with various raw aqueous solutions, including feed solutions of neutral solutes, inorganic salts or salt mixtures to estimate pore size, characterize charge properties and evaluate water hardness removal. The flux and rejection of each raw aqueous solution were measured accordingly. The solute rejection R (%) is calculated according to the following formula:
wherein the external diameter/internal diameter of the hollow fiber membrane filaments is 1.1/0.7 mm.
Pure water flux and pore size of ultrafiltration membrane: 300LMH/BAR, 2.4 kDa.
The pure water flux of the nanofiltration membrane is 28LMH/BAR, 1.0 kDa.
Specific examples of applications are:
nanofiltration membrane aperture test experiment:
the pore size characterization of the nanofiltration membranes was tested using the MWCO test method. 1000ppm PEG solution is prepared, and the molecular weight distribution is from 1000 to 10000. The hollow fiber low pressure nanofiltration membrane of preparation example 1 of the present invention was operated on the above-mentioned test equipment for 1 hour at a test pressure of 1bar and a test temperature of 25 degrees celsius, and the PEG in the raw solution and the filtrate were subjected to molecular weight distribution test by Gel Permeation Chromatography (GPC).
The pore size of the hollow fiber nanofiltration membrane is defined by the molecular weight of PEG with a rejection of 90%. The following table is the test results of the aperture, pure water flux and cut-off molecular weight of the hollow fiber nanofiltration membrane. Take the first preparation example as an example.
Taking a magnesium chloride solution as a raw water solution:
preparing a 300ppm magnesium chloride solution, testing the pressure at 2-5bar and the temperature at 25 ℃, wherein the net waste ratio is 1: 1. the hollow fiber low-pressure nanofiltration membrane of the invention is operated on the test equipment, the flux is 18-25lmh/bar, and the magnesium ion rejection rate is 90-95%.
Taking a calcium chloride solution as a raw water solution:
preparing 300ppm calcium chloride solution, testing pressure of 2-5bar, testing temperature of 25 ℃, net waste ratio of 1: 1. the hollow fiber low-pressure nanofiltration membrane of the invention is operated on the test equipment, the flux is 18-25lmh/bar, and the calcium ion rejection rate is 87-93%.
Using magnesium sulfate solution as raw water solution
Preparing a 300ppm magnesium sulfate solution, testing the pressure at 2-5bar and the temperature at 25 ℃, wherein the net waste ratio is 1: 1. the hollow fiber low-pressure nanofiltration membrane of the invention is operated on the test equipment, the flux is 18-25lmh/bar, and the magnesium ion rejection rate is 75-88%.
And (3) repeatability experiment: taking a magnesium chloride solution as a raw water solution:
the hollow fiber low-pressure nanofiltration membrane is manufactured into 40 membrane components with the diameter of 14.5mm and the length of 260mm, deionized water and 1000ppm magnesium chloride solution are prepared, the hollow fiber low-pressure nanofiltration membrane is operated on the test equipment, the flux is 18-25lmh/bar, the test is repeated, the magnesium ion rejection rate is 88-96%, and the test result is shown in figure 4.
Long-term stability experiments: taking a magnesium chloride solution as a raw water solution:
the hollow fiber low-pressure nanofiltration membrane is manufactured into a membrane component with the diameter of 14.5mm and the length of 260mm, a 1000ppm magnesium chloride solution is prepared, the hollow fiber low-pressure nanofiltration membrane is operated on the test equipment, the test time is 90 days, and the test time is from 11/1/2018 to 1/31/2019. The experimental record in the following FIG. 5 shows that the flux is stabilized at around 15lmh/bar and the magnesium ion rejection rate is around 95%.
The chlorine resistance experiment takes a magnesium chloride solution as a raw water solution
The hollow fiber low-pressure nanofiltration membrane is manufactured into a membrane component with the diameter of 30mm and the length of 360mm, a solution of 10ppm of sodium hypochlorite and 300ppm of magnesium chloride is prepared, the hollow fiber low-pressure nanofiltration membrane is operated on the test equipment, the test time is 18 days, the experimental record shows that the flux is stable at about 10lmh/bar, and the TDS rejection rate is about 90 percent, as shown in figure 6.
Tap water softening case 1
The hollow fiber low-pressure nanofiltration membrane obtained in the first preparation embodiment of the invention is manufactured into a filter element with the diameter of 30mm and the length of 360mm, the filter element is directly connected to a tap water faucet of a Qingdao, no pretreatment is needed, and the net-to-waste ratio is set to be 1: 1. the water pressure of tap water is 3bar, the TDS of source water is about 500ppm, the hardness is 360ppm, and the filtration result shows that the hardness of the water produced by the nanofiltration membrane is only 30ppm, and the TDS is reduced to 240 ppm. This means that the hollow fiber nanofiltration membrane has no obvious interception effect on monovalent ions. Nanofiltration produced water belongs to softened water, but a certain amount of minerals (potassium, sodium, magnesium and calcium) are retained in the nanofiltration produced water, so that the nanofiltration produced water is more suitable for drinking.
Tap water softening case 2
The hollow fiber low-pressure nanofiltration membrane obtained in the first preparation embodiment of the invention is manufactured into a filter element with the diameter of 14.5mm and the length of 260mm, the filter element is directly connected to a tap water tap of Nanjing, and the net-to-waste ratio is set to be 1: 1. the water pressure of tap water is 3bar, the TDS of source water is about 450ppm, the hardness is 250ppm, and the filtration result shows that the hardness of the water produced by the nanofiltration membrane is 49.8ppm, and the TDS is reduced to 257 ppm.
Tap water softening case 2
The hollow fiber low-pressure nanofiltration membrane obtained in the first preparation embodiment of the invention is manufactured into a water purification filter element with the diameter of 90mm and the length of 380mm, and the water purification filter element is tested by testing equipment in Hangzhou, and the net-to-waste ratio is set to be 1: 1. the water inlet pressure is 3bar, the TDS of the source water is about 154ppm, the hardness is 85.2ppm, and the filtration result shows that the hardness of the nanofiltration membrane produced water is 11.7ppm, and the TDS is reduced to 58.2 ppm.
The present invention is not limited to the above-mentioned preferred embodiments, and any other products in various forms can be obtained by anyone in the light of the present invention, but any changes in the shape or structure thereof, which have the same or similar technical solutions as those of the present application, fall within the protection scope of the present invention.
Claims (5)
1. The preparation method of the internal pressure type composite hollow fiber nanofiltration membrane yarn is characterized by comprising the following steps of:
s1 preparation of hollow fiber ultrafiltration membrane:
respectively injecting the membrane casting feed liquid and the core liquid into a spinning nozzle through a membrane casting liquid channel and a core liquid channel by a gear pump, extruding a hollow tubular liquid membrane through a membrane casting liquid port and a core liquid port of the spinning nozzle, allowing the hollow tubular liquid membrane to pass through the air section height and enter a coagulation bath pool for solidification, soaking at constant temperature to remove a solvent to obtain a hollow fiber membrane base membrane, sequentially passing through water and glycerol for soaking the hollow fiber membrane base membrane, and then drying in the air to obtain a hollow fiber ultrafiltration base membrane;
the casting membrane solution is prepared from a hydrophilic polymer, a solvent and a solution assistant solution, wherein the hydrophilic polymer is selected from any one of polyether sulfone, polysulfone or a material containing sulfonic acid groups, the solvent is selected from at least one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and the solution assistant solution comprises at least one of polyethylene glycol and polyvinylpyrrolidone;
the core liquid consists of a solvent, a non-solvent and a core liquid auxiliary agent, wherein the solvent comprises one of dimethylformamide, dimethylacetamide and N-methylpyrrolidone, the non-solvent comprises one of water and ethanol, and the auxiliary agent comprises at least one of ethylene glycol and glutaraldehyde;
s2 preparation of dense selective layer of aromatic polyamide:
forming a crosslinked polyamine compact selective layer on the skin layer of the hollow fiber ultrafiltration basal membrane through crosslinking, wherein the crosslinking system comprises a first crosslinking solution and a second crosslinking solution, and the first crosslinking solution comprises: the first high molecular polymer is selected from at least one of polyethyleneimine, polyallylamine and polyamide, the additive is selected from at least one of sodium dodecyl benzene sulfonate and sodium dodecyl sulfate, the second crosslinking solution comprises glutaraldehyde and a solvent, the forming mechanism of the crosslinked polyamine compact selective layer is that the polyamine polymer is uniformly coated on the inner surface of the hollow fiber membrane, and the amino functional group is subjected to polycondensation reaction under the action of glutaraldehyde.
2. The method for preparing an internal pressure type composite hollow fiber nanofiltration membrane yarn according to claim 1, wherein the step S2 further comprises:
s21: preparing a first crosslinking solution and a second crosslinking solution according to a compact selective layer formula;
s22: soaking the hollow fiber ultrafiltration base membrane obtained in the step S1 in a first cross-linking solution at the temperature of 15-35 ℃, taking out after soaking for 1-60 minutes, and removing the redundant first cross-linking solution;
s23: soaking the hollow fiber ultrafiltration base membrane treated in the step S22 in a second crosslinking solution at 15-35 ℃ for 1-60 minutes, taking out, and removing the redundant second crosslinking solution;
s24: immersing the hollow fiber ultrafiltration basal membrane treated in the step S23 in reverse osmosis water, controlling the temperature at 15-85 ℃, and taking out after immersing for 1-48 hours;
s25: immersing the hollow fiber ultrafiltration basal membrane treated in the step S24 in a glycerol solution, controlling the temperature at 15-45 ℃, and taking out after immersing for 12-48 hours;
s26: and (4) drying the hollow fiber ultrafiltration basal membrane treated in the step S25 in air at the temperature of 20-30 ℃ to obtain the internal pressure type composite hollow fiber nanofiltration membrane.
3. The method for preparing an internal pressure type composite hollow fiber nanofiltration membrane filament according to claim 1, wherein the content of the hydrophilic polymer is 5-30 wt%, and the molecular weight is between 500000-800000 Da; the formulation of the first crosslinking solution includes: the composition of the three formulas is 100 percent according to the weight percentage: 0.1 to 5 percent of first high molecular polymer; 95-99.9% of solvent; 0.01 to 0.05 percent of additive; the formulation of the second crosslinking solution comprises: the combination of the two formulas is 100 percent according to the weight percentage: 0.1 to 20 percent of glutaraldehyde; solvent: 80 to 99.9 percent.
4. An internal pressure type composite hollow fiber nanofiltration membrane wire, which is prepared by the preparation method of the internal pressure type composite hollow fiber nanofiltration membrane wire according to any one of claims 1 to 3, is characterized by comprising a hollow fiber ultrafiltration base membrane prepared from polyether sulfone, polysulfone or a material containing sulfonic acid groups, and a polyamine compact layer obtained by reacting amino functional groups with glutaraldehyde, wherein the amino functional groups are subjected to polycondensation reaction under the action of the glutaraldehyde.
5. The internal pressure type composite hollow fiber nanofiltration membrane yarn according to claim 4, wherein the inner layer is a hollow fiber ultrafiltration base membrane mainly composed of polyethersulfone, and a polyamine dense layer is formed on the inner wall of the hollow fiber ultrafiltration base membrane.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269301A (en) * | 2008-05-09 | 2008-09-24 | 天津膜天膜工程技术有限公司 | Method for preparing internal air pressure type hollow fiber compound film component |
| CN105396470A (en) * | 2015-12-10 | 2016-03-16 | 广州中国科学院先进技术研究所 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN109692577A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The cross-linking modified preparation method of total coating of hollow fiber ultrafiltration membrane |
| CN110026096A (en) * | 2019-03-15 | 2019-07-19 | 浙江工业大学 | Preparation method of PS/SPES hollow fiber membrane for treating dyeing wastewater |
| CN110141980A (en) * | 2019-05-28 | 2019-08-20 | 迈博瑞生物膜技术（南通）有限公司 | A kind of inner pressed hollow fiber nanofiltration membrane and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321727C (en) * | 2004-11-12 | 2007-06-20 | 国家海洋局杭州水处理技术研究开发中心 | Novel reverse osmosis antioxidant compound membrane of polyamide and its preparing method |
| CN107029555A (en) * | 2017-04-19 | 2017-08-11 | 大连理工大学 | A kind of solvent resistant NF membrane and preparation method thereof |
| US10646829B2 (en) * | 2017-06-22 | 2020-05-12 | Teledyne Scientific & Imaging, Llc | High flux, chlorine resistant coating for sulfate removal membranes |
| KR101979567B1 (en) * | 2017-09-01 | 2019-05-20 | 고려대학교 산학협력단 | Thin Film Composite Membranes with Surface Pattern Structures for Excellent Antifouling Resistance |
| CN109692576A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The interface-cross-linked modification method for preparing of hollow fiber ultrafiltration membrane |
-
2019
- 2019-12-09 CN CN201911250982.9A patent/CN110917912B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101269301A (en) * | 2008-05-09 | 2008-09-24 | 天津膜天膜工程技术有限公司 | Method for preparing internal air pressure type hollow fiber compound film component |
| CN105396470A (en) * | 2015-12-10 | 2016-03-16 | 广州中国科学院先进技术研究所 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN109692577A (en) * | 2017-10-20 | 2019-04-30 | 宁波方太厨具有限公司 | The cross-linking modified preparation method of total coating of hollow fiber ultrafiltration membrane |
| CN110026096A (en) * | 2019-03-15 | 2019-07-19 | 浙江工业大学 | Preparation method of PS/SPES hollow fiber membrane for treating dyeing wastewater |
| CN110141980A (en) * | 2019-05-28 | 2019-08-20 | 迈博瑞生物膜技术（南通）有限公司 | A kind of inner pressed hollow fiber nanofiltration membrane and preparation method thereof |
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Effective date of registration: 20231213 Address after: Room 506, Building 5, High tech Industrial Innovation Park, No.13-19 Ketai Second Road, Guangzhou Private Science and Technology Park, Baiyun District, Guangzhou City, Guangdong Province, 510445 Patentee after: Beina New Materials (Guangzhou) Co.,Ltd. Address before: Room 333, Zhongguancun Software Park, 3rd Floor, Building 1, No. 7 Yingcui Road, Jiangning Development Zone, Jiangning District, Nanjing City, Jiangsu Province, 211100 (Jiangning Development Zone) Patentee before: Nanjing Weiyi Environmental Protection Center (Limited Partnership) |
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